TY - JOUR

T1 - Switching Competition between Electron and Energy Transfers in Porphyrin–Fullerene Dyads

AU - Strelnikov , Artem A.

AU - Konev, Alexander S.

AU - Levin, Oleg V.

AU - Khlebnikov, Alexander F.

AU - Iwasaki, Atsushi

AU - Yamanouchi, Kaoru

AU - Tkachenko, Nikolai

PY - 2020/12/3

Y1 - 2020/12/3

N2 - Porphyrin–fullerene dyads were intensively studied as molecular donor–acceptor systems providing efficient photoinduced charge separation (CS). A practical advantage of the dyads is the possibility to tune its CS process by the porphyrin periphery modification, which allows one to optimize the dyad for particular applications. However, this tuning process is typically composed of a series of trial stages involving the development of complex synthetic schemes. To address the issue, we synthesized a series of dyads with properties switching between electron and energy transfer in both polar (benzonitrile) and nonpolar (toluene) media and developed a computation procedure with sufficient reliability by which we can predict the CS properties of the dyad in different media and design new dyads. The dyads photochemistry was established by conducting ultrafast transient absorption studies in toluene, anisole, and benzonitrile. The most crucial step in computational modeling was to establish a procedure for correction of the electronic-state energies obtained by DFT so that the effects of the electron correlation and the long-range interactions are properly incorporated. We also carried out standard electrochemical measurements and show that our computation approach predicts better thermodynamics of the dyads in different solvents.

AB - Porphyrin–fullerene dyads were intensively studied as molecular donor–acceptor systems providing efficient photoinduced charge separation (CS). A practical advantage of the dyads is the possibility to tune its CS process by the porphyrin periphery modification, which allows one to optimize the dyad for particular applications. However, this tuning process is typically composed of a series of trial stages involving the development of complex synthetic schemes. To address the issue, we synthesized a series of dyads with properties switching between electron and energy transfer in both polar (benzonitrile) and nonpolar (toluene) media and developed a computation procedure with sufficient reliability by which we can predict the CS properties of the dyad in different media and design new dyads. The dyads photochemistry was established by conducting ultrafast transient absorption studies in toluene, anisole, and benzonitrile. The most crucial step in computational modeling was to establish a procedure for correction of the electronic-state energies obtained by DFT so that the effects of the electron correlation and the long-range interactions are properly incorporated. We also carried out standard electrochemical measurements and show that our computation approach predicts better thermodynamics of the dyads in different solvents.

UR - http://www.scopus.com/inward/record.url?scp=85097210678&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/746c6fd2-389d-38c1-b86b-67e992cd0765/

U2 - 10.1021/acs.jpcb.0c06931

DO - 10.1021/acs.jpcb.0c06931

M3 - Article

VL - 124

SP - 10899

EP - 10912

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

SN - 1520-6106

IS - 48

ER -